CN101173025A - Magnetic temperature sensing nano-particle with bioavailability and synthesizing method thereof - Google Patents
Magnetic temperature sensing nano-particle with bioavailability and synthesizing method thereof Download PDFInfo
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- CN101173025A CN101173025A CNA2007100310667A CN200710031066A CN101173025A CN 101173025 A CN101173025 A CN 101173025A CN A2007100310667 A CNA2007100310667 A CN A2007100310667A CN 200710031066 A CN200710031066 A CN 200710031066A CN 101173025 A CN101173025 A CN 101173025A
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Abstract
The invention relates to a magnetic thermometer nm particle with biocompatibility, which has biocompatibility, and double response properties of magnetism and thermometer property, and the particle diameter thereof is 20 to 60 nm, and the magnetic responsibility is strong, and magnetic saturation intensity is 10.0 to 27.0 emu/g. The synthetic method of the magnetic thermometer nm particle with biocompatibility comprises: firstly, adopting chemical coprecipitation method to prepare magnetic Fe3O4 nm particle, and using silane coupler to hold surface modification, and then using the modified magnetic Fe3O4 nm particle as a seed, and having polyreaction with dextran, N-isopropyl acrylamide, finally obtaining the magnetic thermometer nm particle with biocompatibility. The magnetic thermometer nm particle with biocompatibility synchronously has double responses of magnetism and thermometer property, and has wide application prospect in the fields of drug release, protein and enzyme separation.
Description
Technical field
The invention belongs to the technical field of environment-responsive material, particularly a kind of magnetic temperature sensing nano-particle and synthetic method thereof with biocompatibility.
Background technology
The magnetic high-molecular nanoparticle is a kind of application environment-responsive material more widely, and it is meant the ultrafine particulate that contains magneticmetal or metal oxide and the polymer particle with magnetic responsiveness.The magnetic high-molecular nanoparticle removes has the characteristic of high molecular particle, can be by copolymerization, surface modification, give its multiple reactive functional group in surface, also because of having magnetic, can under the effect of externally-applied magnetic field, separate easily, exactly because have in the presence of external magnetic field and can directedly arrive this property of specific region, it equally with other environmental response polymer is had a wide range of applications in fields such as cellular segregation, immobilized enzyme, immunodiagnosis and neoplasm targeted therapies.
High molecule magnetic microsphere and preparation thereof, the investigator attaches great importance to both at home and abroad.Chinese patent CN1290524 discloses a kind of preparation method and its usage of chitosan microball, Chinese patent CN1600800 and Chinese patent CN1763126 disclose the composite method for preparing polymer microsphere of a kind of polysaccharide respectively, the weak point of above-mentioned patent is that these methods are the polysaccharide magnetic microspheres that obtain by crosslinked coated magnetic particle with natural biologic material, wherein combining between magnetic particle and the polymer mainly is that the magnetic responsiveness of resulting magnetic microsphere is not too strong by Van der Waals force, hydrogen bond, covalent linkage, sequestering action etc.Chinese patent CN1995144 discloses a kind of synthetic method of magnetic temperature-sensitive nano particle, synthesized a kind of magnetic temperature-sensitive nano particle with magnetic and temperature sensitive double-response performance, its weak point is that this magnetic temperature-sensitive nano particle does not have biocompatibility, and its application at biomedical aspect is restricted.
Development along with biomedical sector research has biocompatibility, the multiple response polymer particle more and more causes people's attention, and exploitation biocompatibility, functionalization, intelligent polymer particle are one of important research directions of polymer particle.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art part, a kind of magnetic temperature sensing nano-particle with biocompatibility is provided, this magnetic temperature sensing nano-particle with biocompatibility has magnetic and temperature sensitive property double-response simultaneously, and has broad application prospects at the aspects such as separation of medicine controlled releasing, protein, enzyme.
Another object of the present invention is to provide above-mentioned synthetic method with magnetic temperature sensing nano-particle of biocompatibility.
Purpose of the present invention is realized by following technical proposals: a kind of synthetic method with magnetic temperature sensing nano-particle of biocompatibility comprises the steps: at first to adopt chemical coprecipitation to prepare magnetic Fe
3O
4Nano particle, and with silane coupler it is carried out surface modification, then with the magnetic Fe after the modification
3O
4Nano particle is seed, carries out polymerisation with the glucan with good biocompatibility, monomer NIPA (NIPAM) with temperature sensitivity, prepares the magnetic temperature sensing nano-particle with biocompatibility.Adopt silane coupler to magnetic Fe
3O
4The purpose that nano particle carries out surface modification is in magnetic Fe
3O
4Polymerisable group is introduced on the surface of nano particle.
Above-mentioned synthetic method with magnetic temperature sensing nano-particle of biocompatibility comprises the steps:
(1) preparation magnetic Fe
3O
4Nano particle: with 0.05g～0.50g FeCl
24H
2O and 0.15g～1.35gFeCl
36H
2O is dissolved in 200～350mL water simultaneously, adds aqueous slkali under 50～60 ℃, nitrogen protection, stirs, and makes system pH=11～12, and 75～85 ℃ of reactions 40～70 minutes, Magnetic Isolation was washed till neutrality with product water, and drying obtains magnetic Fe
3O
4Nano particle;
(2) magnetic Fe
3O
4The surface modification of nano particle: with 0.1～0.3g magnetic Fe
3O
4Nano particle joins in alcohol/aqueous solution of 40mL, and ultrasonic dispersion treatment is removed magnetic Fe
3O
4Nanoparticle surface impurity, the magnetic Fe that obtains after the Magnetic Isolation
3O
4Nano particle adds alcohol/aqueous solution again and is made into suspension, makes suspension vol reach 40mL, and adding volume is the silane coupler of suspension vol 1～3%, after stirring, reacts 5～7 hours under 60～70 ℃ of conditions, obtains silane coupler modified magnetic Fe
3O
4Alcohol/the aqueous dispersions of nano particle; It is 0.8: 1～1.2: 1 as the alcohol of decentralized medium and the volume ratio of water in described alcohol/aqueous solution;
(3) preparation has the magnetic temperature sensing nano-particle of biocompatibility: in silane coupler modified magnetic Fe
3O
4In the alcohol/aqueous dispersions of nano particle; adding 0.3～1.0g NIPA (NIPAM) and 0.3～0.5g glucan fully dissolves; add 0.02～0.05g initator+0.01～0.02g promoter and be dissolved in the solution in 1.0～5.0mL water; add 0.02～0.05g crosslinking agent after 8～10 minutes; under nitrogen protection, stirred 30～50 minutes; under 60～80 ℃ of conditions, reacted 6～8 hours; product water, alcohol are washed successively to neutrality; separation and purification; at normal temperatures dry, make the magnetic temperature sensing nano-particle with biocompatibility.
Alkaline solution in the described step (1) is a kind of in the solution such as ammoniacal liquor, sodium hydroxide or potassium hydroxide, and concentration is 4～4.5mol/L.
Alcohol is one or both in methyl alcohol, ethanol or the isopropyl alcohol etc. in alcohol/aqueous solution in the described step (2); Special preferred water is distilled water.
Silane coupling agent in the described step (2) is 3-(methacryloxypropyl) propyl trimethoxy silicane.
Initiator in the described step (3) is Potassium Persulphate, ammonium persulphate or ceric ammonium nitrate etc.
Promotor in the described step (3) is Tetramethyl Ethylene Diamine.
Linking agent in the described step (3) is macromolecule crosslink agent N,N methylene bis acrylamide commonly used.
The preferred especially dry vacuum-drying that is.
By the preparation-obtained magnetic temperature sensing nano-particle of aforesaid method with biocompatibility, it is characterized in that this nanoparticle has biocompatibility, and have magnetic and a temperature sensitive property double-response performance, its particle diameter is 20～60 nanometers, magnetic responsiveness is strong, and magnetic saturation intensity is 10.0～27.0emu/g.
The present invention compared with prior art has following advantage and beneficial effect:
1, institute's synthetic magnetic temperature sensing nano-particle has biocompatibility, and has magnetic and temperature sensitive property double-response performance;
2, with silane coupler to Fe
3O
4The modifying surface of nano particle had both solved magnetic Fe
3O
4Nano particle disperses bad shortcoming, again in magnetic Fe
3O
4Nanoparticle surface has been introduced polymerizable groups;
3, synthetic method is simple and reliable, does not use emulsifying agent in the building-up process;
4, institute's synthetic magnetic temperature sensing nano-particle has stronger magnetic responsiveness, and magnetic saturation intensity is 10.0～27.0emu/g, presents superparamagnetism.
Description of drawings
Fig. 1 is the prepared infrared spectrogram with magnetic temperature sensing nano-particle of biocompatibility of the present invention.
Fig. 2 is the prepared sem photograph with magnetic temperature sensing nano-particle of biocompatibility of the present invention.
Fig. 3 is the prepared magnetic hysteresis loop figure with magnetic temperature sensing nano-particle of biocompatibility of the present invention.
Fig. 4 is the prepared ultraviolet permeability figure of magnetic temperature sensing nano-particle under differing temps with biocompatibility of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) preparation magnetic Fe
3O
4Nano particle: take by weighing 0.20g FeCl
24H
2O and 0.50gFeCl
36H
2O is dissolved in the 200mL distilled water simultaneously, and in the time of 50 ℃, next time property adding of nitrogen protection 4.0mol/L NaOH solution, vigorous stirring makes system pH=11.80 ℃ of reactions 60 minutes, Magnetic Isolation repeatedly was washed till neutrality with distilled water with product, in 60 ℃ of vacuum drying ovens dry 72 hours then, obtained magnetic Fe
3O
4Nano particle;
(2) magnetic Fe
3O
4The surface modification of nano particle: take by weighing the 0.2g magnetic Fe
3O
4It is that ultrasonic dispersion treatment 30min removes magnetic Fe in ethanol/distilled water solution of 1: 1 as the volume ratio of the ethanol of decentralized medium and distilled water that nano particle joins 40mL
3O
4Nanoparticle surface impurity.The magnetic Fe that obtains after the Magnetic Isolation
3O
4Nano particle adds ethanol/distilled water solution (volume ratio of ethanol and distilled water is 1: 1) again and is made into suspension, make suspension vol reach 40mL, adding volume is 3-(methacryloxypropyl) propyl trimethoxy silicane of suspension vol 2%, after stirring, reaction is 6 hours under 70 ℃ of conditions, obtains silane coupler modified magnetic Fe
3O
4The ethanol of nano particle and distilled water dispersion liquid;
(3) preparation has the magnetic temperature sensing nano-particle of biocompatibility: in silane coupler modified magnetic Fe
3O
4In the ethanol of nano particle/distilled water dispersion liquid; add 0.3g NIPAM and 0.5g glucan; fully dissolving under condition of nitrogen gas; add 0.02g potassium peroxydisulfate+0.015g tetramethylethylenediamine and be dissolved in the solution in the 1.0mL distilled water; add 0.05g N after 10 minutes; the N-methylene-bisacrylamide stirred 30 minutes under nitrogen protection, and reaction is 7 hours under 70 ℃ of conditions.Product washs to neutrality successively through distilled water, ethanol, separation and purification, and vacuum-drying at normal temperatures 7 days can make the magnetic temperature sensing nano-particle with biocompatibility.
As shown in Figure 1, glucan, NIPAM and Fe have been shown in the infrared spectrogram of prepared magnetic temperature sensing nano-particle with biocompatibility
3O
4Characteristic absorption peak, illustrate that glucan, NIPAM have been bonded to magnetic Fe
3O
4On the nano particle.
As shown in Figure 2, the particle diameter of the Scanning Electron Microscope photos reveal magnetic temperature sensing nano-particle of prepared magnetic temperature sensing nano-particle with biocompatibility is approximately 40nm, and is better dispersed.
As shown in Figure 3, prepared magnetic hysteresis loop figure with magnetic temperature sensing nano-particle of biocompatibility shows that saturation magnetization is 27.0emu/g, illustrates that prepared magnetic temperature sensing nano-particle has stronger magnetic responsiveness, presents superparamagnetism.
As shown in Figure 4, prepared ultraviolet permeability figure with magnetic temperature sensing nano-particle of biocompatibility shows that transmitance varies with temperature and changes, flex point has appearred near 34 ℃, the lower critical solution temperature of this and used temperature sensing material poly N-isopropyl acrylamide is close, illustrates that prepared magnetic temperature sensing nano-particle has the temperature sensitive performance.
Embodiment 2
(1) preparation magnetic Fe
3O
4Nano particle: take by weighing 0.05g FeCl
24H
2O and 0.15gFeCl
36H
2O is dissolved in the 200mL water simultaneously, and in the time of 50 ℃, next time property adding of nitrogen protection 4.5mol/L ammonia spirit, vigorous stirring makes system pH=12.75 ℃ of reactions 70 minutes, Magnetic Isolation repeatedly was washed till neutrality with deionized water with product, in 60 ℃ of vacuum drying ovens dry 72 hours then, obtained magnetic Fe
3O
4Nano particle;
(2) magnetic Fe
3O
4The surface modification of nano particle: take by weighing the 0.3g magnetic Fe
3O
4It is that ultrasonic dispersion treatment 30min removes magnetic Fe in ethanol/distilled water solution of 1: 1 as the volume ratio of the ethanol of decentralized medium and distilled water that nano particle joins 40mL
3O
4Nanoparticle surface impurity.The magnetic Fe that obtains after the Magnetic Isolation
3O
4Nano particle adds ethanol/distilled water solution (volume ratio of ethanol and distilled water is 1: 1) again and is made into suspension, make suspension vol reach 40mL, 3-(methacryloxypropyl) propyl trimethoxy silicane that adds suspension vol 3%, after stirring, reaction is 7 hours under 60 ℃ of conditions, obtains silane coupler modified magnetic Fe
3O
4The ethanol of nano particle/distilled water dispersion liquid;
(3) preparation has the magnetic temperature sensing nano-particle of biocompatibility: in silane coupler modified magnetic Fe
3O
4In the ethanol of nano particle/distilled water dispersion liquid; add 0.5g NIPAM and 0.5g glucan; fully dissolving under condition of nitrogen gas; add 0.05g ammonium persulfate+0.01g tetramethylethylenediamine and be dissolved in the solution in the 5.0mL distilled water; add 0.05g N after 8 minutes; the N-methylene-bisacrylamide stirred 40 minutes under nitrogen protection, and reaction is 6 hours under 80 ℃ of conditions.Product washs to neutrality successively through distilled water, ethanol, separation and purification, and vacuum-drying at normal temperatures 7 days makes the magnetic temperature sensing nano-particle with biocompatibility.
Obtained magnetic temperature sensing nano-particle particle diameter with biocompatibility is 30 nanometers, and magnetic saturation intensity is 25.0emu/g.
Embodiment 3:
(1) preparation magnetic Fe
3O
4Nanoparticle: take by weighing 0.10g FeCl
24H
2O and 0.40g FeCl
36H
2O is dissolved in the 200 mL water simultaneously, and in the time of 55 ℃, nitrogen protection property adding next time 4.5mol/L NaOH solution, vigorous stirring makes system pH=11.85 ℃ of reactions 40 minutes, Magnetic Isolation repeatedly was washed till neutrality with deionized water with product, in 60 ℃ of vacuum drying ovens dry 72 hours then, obtained magnetic Fe
3O
4Nano particle;
(2) magnetic Fe
3O
4The surface modification of nano particle: take by weighing the 0.1g magnetic Fe
3O
4It is that ultrasonic dispersion treatment 30min removes magnetic Fe in 1.2: 1 the methanol/water solution as the volume ratio of the methyl alcohol of decentralized medium and water that nano particle joins 40mL
3O
4Nanoparticle surface impurity.The magnetic Fe that obtains after the Magnetic Isolation
3O
4Nano particle adds methanol/water solution (volume ratio of methyl alcohol and water is 1.2: 1) again and is made into suspension, make suspension vol reach 40mL, 3-(methacryloxypropyl) propyl trimethoxy silicane that adds suspension vol 1%, after stirring, reaction is 5 hours under 70 ℃ of conditions, obtains silane coupler modified magnetic Fe
3O
4The methanol/water dispersion liquid of nano particle;
(3) preparation has the magnetic temperature sensing nano-particle of biocompatibility: in silane coupler modified magnetic Fe
3O
4In the methanol/water dispersion liquid of nano particle; add 0.7g NIPAM and 0.3g glucan; fully dissolving under condition of nitrogen gas; add 0.04g potassium peroxydisulfate+0.02g tetramethylethylenediamine and be dissolved in the solution in the 5.0mL distilled water; add 0.04g N after 10 minutes; the N-methylene-bisacrylamide stirred 50 minutes under nitrogen protection, and reaction is 8 hours under 60 ℃ of conditions.Product washs to neutrality successively through distilled water, methyl alcohol, separation and purification, and vacuum-drying at normal temperatures 7 days makes the magnetic temperature sensing nano-particle with biocompatibility.
Obtained magnetic temperature sensing nano-particle particle diameter with biocompatibility is 20 nanometers, and magnetic saturation intensity is 10.0emu/g.
Embodiment 4:
(1) preparation magnetic Fe
3O
4Nanoparticle: take by weighing 0.30g FeCl
24H
2O and 0.80g FeCl
36H
2O is dissolved in the 250mL water simultaneously, and in the time of 60 ℃, nitrogen protection property adding next time 4.2mol/L KOH solution, vigorous stirring makes system pH=11.80 ℃ of reactions 60 minutes, Magnetic Isolation repeatedly was washed till neutrality with deionized water with product, in 60 ℃ of vacuum drying ovens dry 72 hours then, obtained magnetic Fe
3O
4Nano particle;
(2) magnetic Fe
3O
4The surface modification of nano particle: take by weighing the 0.2g magnetic Fe
3O
4It is that ultrasonic dispersion treatment 30min removes magnetic Fe in 0.8: 1 the ethanol/water solution as the volume ratio of the ethanol of decentralized medium and water that nano particle joins 40mL
3O
4Nanoparticle surface impurity.The magnetic Fe that obtains after the Magnetic Isolation
3O
4Nano particle adds ethanol/water solution (volume ratio of ethanol and water is 0.8: 1) again and is made into suspension, make suspension vol reach 40mL, 3-(methacryloxypropyl) propyl trimethoxy silicane that adds suspension vol 3%, after stirring, reaction is 6 hours under 70 ℃ of conditions, obtains silane coupler modified magnetic Fe
3O
4The ethanol/water dispersion liquid of nano particle;
(3) preparation has the magnetic temperature sensing nano-particle of biocompatibility: in silane coupler modified magnetic Fe
3O
4In the ethanol/water dispersion liquid of nano particle; add 0.3g NIPAM and 0.4g glucan; fully dissolving under condition of nitrogen gas; add 0.03g ammonium ceric nitrate+0.02g tetramethylethylenediamine and be dissolved in the solution in the 4.0mL distilled water; add 0.02g N after 10 minutes; the N-methylene-bisacrylamide stirred 30 minutes under nitrogen protection, and reaction is 7 hours under 70 ℃ of conditions.Product washs to neutrality successively through distilled water, ethanol, separation and purification, and vacuum-drying at normal temperatures 7 days makes the magnetic temperature sensing nano-particle with biocompatibility.
Obtained magnetic temperature sensing nano-particle particle diameter with biocompatibility is 50 nanometers, and magnetic saturation intensity is 17.0emu/g.
Embodiment 5:
(1) preparation magnetic Fe
3O
4Nanoparticle: take by weighing 0.20g FeCl
24H
2O and 0.60g FeCl
36H
2O is dissolved in the 200mL water simultaneously, and in the time of 50 ℃, nitrogen protection property adding next time 4.0mol/L ammonia soln, vigorous stirring makes system pH=11.80 ℃ of reactions 60 minutes, Magnetic Isolation repeatedly was washed till neutrality with deionized water with product, in 60 ℃ of vacuum drying ovens dry 72 hours then, obtained magnetic Fe
3O
4Nano particle;
(2) magnetic Fe
3O
4The surface modification of nano particle: take by weighing the 0.3g magnetic Fe
3O
4It is that ultrasonic dispersion treatment 30min removes magnetic Fe in 1: 1 the isopropanol/water solution as the volume ratio of the isopropyl alcohol of decentralized medium and water that nano particle joins 40mL
3O
4Nanoparticle surface impurity.The magnetic Fe that obtains after the Magnetic Isolation
3O
4Nano particle adds isopropanol/water solution (volume ratio of isopropyl alcohol and water is 1: 1) again and is made into suspension, make suspension vol reach 40mL, 3-(methacryloxypropyl) propyl trimethoxy silicane that adds suspension vol 3%, after stirring, reaction is 6 hours under 70 ℃ of conditions, obtains silane coupler modified magnetic Fe
3O
4The isopropanol/water dispersion liquid of nano particle;
(3) preparation has the magnetic temperature sensing nano-particle of biocompatibility: in silane coupler modified magnetic Fe
3O
4In the isopropanol/water dispersion liquid of nano particle; add 1.0g NIPAM and 0.5g glucan; fully dissolving under condition of nitrogen gas; add 0.05g potassium peroxydisulfate+0.015g tetramethylethylenediamine and be dissolved in the solution in the 5.0mL distilled water; add 0.05g N after 9 minutes; the N-methylene-bisacrylamide stirred 40 minutes under nitrogen protection, and reaction is 8 hours under 70 ℃ of conditions.Product washs to neutrality successively through distilled water, Virahol, separation and purification, and vacuum-drying at normal temperatures 7 days makes the magnetic temperature sensing nano-particle with biocompatibility.
Obtained magnetic temperature sensing nano-particle particle diameter with biocompatibility is 60 nanometers, and magnetic saturation intensity is 27.0emu/g.
Embodiment 6
(1) preparation magnetic Fe
3O
4Nanoparticle: take by weighing 0.50g FeCl
24H
2O and 1.35g FeCl
36H
2O is dissolved in the 350mL water simultaneously, and in the time of 55 ℃, nitrogen protection property adding next time 4.0mol/LNaOH solution, vigorous stirring makes system pH=11.80 ℃ of reactions 60 minutes, Magnetic Isolation repeatedly was washed till neutrality with distilled water with product, in 60 ℃ of vacuum drying ovens dry 72 hours then, obtained magnetic Fe
3O
4Nano particle;
(2) magnetic Fe
3O
4The surface modification of nano particle: take by weighing the 0.2g magnetic Fe
3O
4It is that ultrasonic dispersion treatment 30min removes magnetic Fe in 1: 1 the methyl alcohol, ethanol/distilled water solution as the volume ratio of the methyl alcohol+ethanol of decentralized medium and distilled water that nano particle joins 40mL
3O
4Nanoparticle surface impurity.The magnetic Fe that obtains after the Magnetic Isolation
3O
4Nano particle adds methyl alcohol+ethanol/distilled water solution (volume ratio of methyl alcohol+ethanol and distilled water is 1: 1) again and is made into suspension, make suspension vol reach 40mL, adding volume is 3-(methacryloxypropyl) propyl trimethoxy silicane of suspension vol 2%, after stirring, reaction is 7 hours under 60 ℃ of conditions, obtains silane coupler modified magnetic Fe
3O
4Methyl alcohol+the ethanol of nano particle/distilled water dispersion liquid;
(3) preparation has the magnetic temperature sensing nano-particle of biocompatibility: in silane coupler modified magnetic Fe
3O
4In the methyl alcohol+ethanol of nano particle/distilled water dispersion liquid; add 0.5g NIPAM and 0.3g glucan; fully dissolving under condition of nitrogen gas; adding 0.02g potassium peroxydisulfate and 0.015g tetramethylethylenediamine are dissolved in the solution in the 1.0mL distilled water; add 0.03g N after 10 minutes; the N-methylene-bisacrylamide stirred 30 minutes under nitrogen protection, and reaction is 7 hours under 60 ℃ of conditions.Product washs to neutrality successively through distilled water, methyl alcohol, ethanol, separation and purification, and vacuum-drying at normal temperatures 7 days can make the magnetic temperature sensing nano-particle with biocompatibility.
Obtained magnetic temperature sensing nano-particle particle diameter with biocompatibility is 45 nanometers, and magnetic saturation intensity is 27.0emu/g.
Embodiment 7
(1) preparation magnetic Fe
3O
4Nanoparticle: take by weighing 0.40g FeCl
24H
2O and 1.20g FeCl
36H
2O is dissolved in the 300mL water simultaneously, and in the time of 60 ℃, nitrogen protection property adding next time 4.5mol/L KOH solution, vigorous stirring makes system pH=12.85 ℃ of reactions 50 minutes, Magnetic Isolation repeatedly was washed till neutrality with distilled water with product, in 60 ℃ of vacuum drying ovens dry 72 hours then, obtained magnetic Fe
3O
4Nano particle;
(2) magnetic Fe
3O
4The surface modification of nano particle: take by weighing the 0.1g magnetic Fe
3O
4It is that ultrasonic dispersion treatment 30min removes magnetic Fe in 0.8: 1 the isopropyl alcohol, methyl alcohol/distilled water solution as the volume ratio of the isopropyl alcohol+methyl alcohol of decentralized medium and distilled water that nano particle joins 40mL
3O
4Nanoparticle surface impurity.The magnetic Fe that obtains after the Magnetic Isolation
3O
4Nano particle adds isopropyl alcohol+methyl alcohol/distilled water solution (volume ratio of isopropyl alcohol+methyl alcohol and distilled water is 0.8: 1) again and is made into suspension, make suspension vol reach 40mL, adding volume is 3-(methacryloxypropyl) propyl trimethoxy silicane of suspension vol 1%, after stirring, reaction is 5 hours under 60 ℃ of conditions, obtains silane coupler modified magnetic Fe
3O
4Isopropyl alcohol+the methyl alcohol of nano particle/distilled water dispersion liquid;
(3) preparation has the magnetic temperature sensing nano-particle of biocompatibility: in silane coupler modified magnetic Fe
3O
4In the isopropyl alcohol+methyl alcohol of nano particle/distilled water dispersion liquid; add 0.8g NIPAM and 0.4g glucan; fully dissolving under condition of nitrogen gas; add 0.04g ammonium persulfate+0.02g tetramethylethylenediamine and be dissolved in the solution in the 5.0mL distilled water; add 0.05g N after 8 minutes; the N-methylene-bisacrylamide stirred 30 minutes under nitrogen protection, and reaction is 6 hours under 80 ℃ of conditions.Product washs to neutrality successively through distilled water, Virahol, ethanol, separation and purification, and vacuum-drying at normal temperatures 7 days can make the magnetic temperature sensing nano-particle with biocompatibility.
Obtained magnetic temperature sensing nano-particle particle diameter with biocompatibility is 35 nanometers, and magnetic saturation intensity is 20.0emu/g.
Embodiment 8
(1) preparation magnetic Fe
3O
4Nanoparticle: take by weighing 0.30g FeCl
24H
2O and 0.90g FeCl
36H
2O is dissolved in the 250mL water simultaneously, and in the time of 50 ℃, nitrogen protection property adding next time 4.0mol/L ammonia soln, vigorous stirring makes system pH=11.75 ℃ of reactions 70 minutes, Magnetic Isolation repeatedly was washed till neutrality with distilled water with product, in 60 ℃ of vacuum drying ovens dry 72 hours then, obtained magnetic Fe
3O
4Nano particle;
(2) magnetic Fe
3O
4The surface modification of nano particle: take by weighing the 0.3g magnetic Fe
3O
4It is that ultrasonic dispersion treatment 30min removes magnetic Fe in isopropyl alcohol+ethanol/distilled water solution of 1.2: 1 as the volume ratio of the isopropyl alcohol+ethanol of decentralized medium and distilled water that nano particle joins 40mL
3O
4Nanoparticle surface impurity.The magnetic Fe that obtains after the Magnetic Isolation
3O
4Nano particle adds isopropyl alcohol+ethanol/distilled water solution (volume ratio of isopropyl alcohol+ethanol and distilled water is 1.2: 1) again and is made into suspension, make suspension vol reach 40mL, adding volume is 3-(methacryloxypropyl) propyl trimethoxy silicane of suspension vol 3%, after stirring, reaction is 6 hours under 70 ℃ of conditions, obtains silane coupler modified magnetic Fe
3O
4Isopropyl alcohol+the ethanol of nano particle/distilled water dispersion liquid;
(3) preparation has the magnetic temperature sensing nano-particle of biocompatibility: in silane coupler modified magnetic Fe
3O
4In the isopropyl alcohol of nano particle, the ethanol/distilled water dispersion liquid, add 0.3g NIPAM and 0.5g glucan, fully dissolving under condition of nitrogen gas, add 0.03g ammonium ceric nitrate+0.01g tetramethylethylenediamine and be dissolved in the solution in the 3.0mL distilled water, add 0.02g N after 9 minutes, the N-methylene-bisacrylamide stirred 40 minutes, and reaction is 6 hours under 70 ℃ of conditions.Product washs to neutrality successively through distilled water, Virahol, methyl alcohol, separation and purification, and vacuum-drying at normal temperatures 7 days can make the magnetic temperature sensing nano-particle with biocompatibility.
Obtained magnetic temperature sensing nano-particle particle diameter with biocompatibility is 40 nanometers, and magnetic saturation intensity is 25.0emu/g.
Claims (10)
1. the synthetic method with magnetic temperature sensing nano-particle of biocompatibility comprises the steps: at first to adopt chemical coprecipitation to prepare magnetic Fe
3O
4Nano particle, and with silane coupler it is carried out surface modification, then with the magnetic Fe after the modification
3O
4Nano particle is seed, carries out polymerisation with glucan, NIPA, prepares the magnetic temperature sensing nano-particle with biocompatibility.
2. the synthetic method with magnetic temperature sensing nano-particle of biocompatibility according to claim 1 is characterized in that comprising the steps:
(1) preparation magnetic Fe
3O
4Nano particle: with 0.05g～0.50g FeCl
24H
2O and 0.15g～1.35gFeCl
36H
2O is dissolved in 200～350mL water simultaneously, adds aqueous slkali under 50～60 ℃, nitrogen protection, stirs, and makes system pH=11～12, and 75～85 ℃ of reactions 40～70 minutes, Magnetic Isolation was washed till neutrality with product water, and drying obtains magnetic Fe
3O
4Nano particle;
(2) magnetic Fe
3O
4The surface modification of nano particle: with 0.1～0.3g magnetic Fe
3O
4Nano particle joins in alcohol/aqueous solution of 40mL, and ultrasonic dispersion treatment is removed magnetic Fe
3O
4Nanoparticle surface impurity, the magnetic Fe that obtains after the Magnetic Isolation
3O
4Nano particle adds alcohol/aqueous solution again and is made into suspension, makes suspension vol reach 40mL, and adding volume is the silane coupler of suspension vol 1～3%, after stirring, reacts 5～7 hours under 60～70 ℃ of conditions, obtains silane coupler modified magnetic Fe
3O
4Alcohol/the aqueous dispersions of nano particle; Volume ratio as the alcohol/water of decentralized medium in described alcohol/aqueous solution is 0.8: 1～1.2: 1;
(3) preparation has the magnetic temperature sensing nano-particle of biocompatibility: in silane coupler modified magnetic Fe
3O
4In the alcohol/aqueous dispersions of nano particle; adding 0.3～1.0g NIPA and 0.3～0.5g glucan fully dissolves; add 0.02～0.05g initator+0.01～0.02g promoter and be dissolved in the solution in 1.0～5.0mL water; add 0.02～0.05g crosslinking agent after 8～10 minutes; under nitrogen protection, stirred 30～50 minutes; under 60～80 ℃ of conditions, reacted 6～8 hours; product water, alcohol are washed successively to neutrality; separation and purification; at normal temperatures dry, make the magnetic temperature sensing nano-particle with biocompatibility.
3. the synthetic method with magnetic temperature sensing nano-particle of biocompatibility according to claim 2 is characterized in that: the alkaline solution in the described step (1) is a kind of in ammoniacal liquor, sodium hydroxide or the potassium hydroxide solution, and concentration is 4～4.5mol/L.
4. the synthetic method with magnetic temperature sensing nano-particle of biocompatibility according to claim 2 is characterized in that: alcohol is one or both in methyl alcohol, ethanol or the Virahol in the alcohol/aqueous solution in the described step (2); Described water is distilled water.
5. the synthetic method with magnetic temperature sensing nano-particle of biocompatibility according to claim 2 is characterized in that: the silane coupling agent in the described step (2) is 3-(methacryloxypropyl) propyl trimethoxy silicane.
6. the synthetic method with magnetic temperature sensing nano-particle of biocompatibility according to claim 2 is characterized in that: the initiator in the described step (3) is Potassium Persulphate, ammonium persulphate or ceric ammonium nitrate.
7. the synthetic method with magnetic temperature sensing nano-particle of biocompatibility according to claim 2 is characterized in that: the promotor in the described step (3) is Tetramethyl Ethylene Diamine.
8. the synthetic method with magnetic temperature sensing nano-particle of biocompatibility according to claim 2 is characterized in that: the linking agent in the described step (3) is the macromolecule crosslink agent N,N methylene bis acrylamide.
9. the synthetic method with magnetic temperature sensing nano-particle of biocompatibility according to claim 2 is characterized in that: described drying is vacuum-drying.
10. according to any preparation-obtained magnetic temperature sensing nano-particle with biocompatibility of claim 1～9, it is characterized in that: its particle diameter is 20～60 nanometers, and magnetic saturation intensity is 10.0～27.0emu/g.
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